Lubricating composition



Patented Dec. 9, 1947 LUBBICATING COMPOSITION Delton R. Frey, EastCleveland, Ohio No Drawing. Application December 29, 1941, Serial No.424,823

13 Claims. (Cl. 252-46.?)

This invention relates, as indicated, to the stabilization of liquidhydrocarbon compositions. The term liquid hydrocarbon compositions" asused herein is intended to include liquid compositions which areessentially derivatives of petroleum, naturally occurring oils of thetypes represented by animal, vegetable and marine oil and derivatives ofthe same.

More specifically this invention relates to the stabilization of liquidhydrocarbon compositions which are essentially mineral oil andparticularly mineral oil of the character commonly employed aslubricants. My invention, however, is likewise applicable to thestabilization of lighter fractions of petroleum such as are used forfuels. Liquid hydrocarbon compositions of the character above identifiedare subject during storage, handling and particularly during use, todeterioration which may be occasioned either by oxidation-orpoiymerization, and such deterioration usually proceeds at anaccelerated rate when, for example, the liquid hydrocarbon compositionis subjected to elevated temperatures and similar conditions encounteredwhen the same are used as lubricants in internal combustion engines.

This deterioration, which, as indicated, may occur either duringstorage, handling or use, is generally manifested by discoloration ofthe liquid hydrocarbon body; generation within the body of fiocculentmaterial; the precipitation from the body of the more serioustypes ofdeterioration products such as sludge; and the deposit of varnish orshellac-like deposits on metallic surfaces with which the compositionscome in contact especially during use.

Inasmuch as deterioration is usually accelerated by the severeconditions, such as temperature, to which the hydrocarbon composition issubjected, it will be observed that my invention is particularly'suitedfor the stabilization of hydrocarbon compositions such as minerallubricating oils used as the lubricant in the crank case of internalcombustion engines whether of the ignition or Diesel type. My inventionis particularly applicable to the stabilization of lubricants used inDiesel engines on account of the more severe stresses to which thelubricating composition is subjected in that type of engine.

It is a principal object of my invention therefore to provide for thestabilization of compositions of the character defined in order toreduce the tendency of the same to decomposition, particularly in themanner indicated.

It will also be observed that the addition agents employed for thedescribed purposes, especially when prepared in the manner hereinaftermore specifically defined, are in themselves new compositions of matter.

Other objects of my invention will appear as the description proceeds.

To the accomplishment of the foregoing and related ends, the invention,then, comprises the features hereinafter fully described, andparticularly pointed out in the claims, the following descriptionsetting forth in detail certain illustrative embodiments of theinvention, these being indicative, however, of but a few of the variousways in which the principle of the invention may be employed.

Broadly stated, this invention comprises the stabilization of liquidhydrocarbon compositions of the character previously identified, by theinclusion therein of a minor proportion of an oilsoluble compound havingin the samemolecule a cycloaliphatic radicle and the phosphite radicle.

The compounds contemplated for use by my invention are believed to havethe following structure:

one or more of the radicles A, B and C may be a cycloaliphatic radicle;and when for example the cycloaliphatic radicle is at A, then B and Cmay be the same or different radicles selected from the class consistingof hydrogen, the metals and any organic radicle. The metals which may beused are those which are capable of producing oils oluble derivatives ofthe remainder f the molecule. Generally the polyvalent metals arepreferred and the following metals will be found particularly suitablefor use, the same being arranged in the order of their preference:

Table I Calcium Zinc Magnesium Cadmium Barium Cobalt Beryllium NickelStrontium Tin Aluminum Silver Chromium Copper As previously indicated,any organic radicle.

may be utilized at one of the positions A, B or C (see B or C forillustration where the cycloali- 3 phatic radicie is positioned at A)and in this connection reference may be had to the following table for aclassification and identification of specific organic radicles which maybe utilized for this purpose.

Table II I. Hydrocarbon radicles (A) Alkyl radlcles Amyl (n, iso, sec.and tertiary) Laur l I Ccty (amaubyl Ceryl Montanyl Mellisyl LaoceryiPsyllicyl B lradlcles lhen l E Xenv Naphthyl (alphsand beta-) Allih I(C) radicles (D) Alkylatcd aryl radicies Radicles formed by thealkylation of aryl radicles. such as those listed above B). with any orthe alkyl radicles. e. f those lsted above (A), or with any or the la]owing:

Methyl Ethyl Prupyl (n-. and l'o-) Butyl (n-, isoand sec-) Spefiificexamples of alkylated aryl radlclel are as o uws:

Phcnyl-ethyl Phenyl-amyl Phenyl-lauryl Phcnyi-cetyl Naphthyiethyl (1i)Cyelo-alkylated alkyl radlcles, e. 5.,

Nuphthenyl Hexahydrohenzyl Cyclotexyl-etiiyl Cyclohexyl-amyl (I)Arylated cyclo-nikyi radicles, e. g.,

Phcnyl-cyclohexyl Xcnyl-cyclotexyl Nophthyl-cyciohexyl (J) Mixedradicies e.g.,

-. Methylcyciolnexyl-phenyl Amylcycloifexyl-fhenyl Cyclohexyl-cresyCyclohexyl-xylyl Cyclobexyl amyl-phenyl Cyclohexyi-bcnzylXylyl-cycloiexyl Lauryihenylcyclohex'yl Cetyl-p enylcyeiohexylPhenyi-methylcyclolzexyl Phenyl-amylcyclotexyl Xyiyl-methylcyclohexyiBenzyl-eyclohexyi Benzyi-meth lcyclohexyl Methylcyclo exyl-amylMethylcyclohexyl-lauryl col) (B) the ketone type, e. g.,

(C) 0! ester type,

erived from by the removal of the hydroxyl group, as (or example, by theremoval of the hydroxyl group from ti.e following esters:

(l) Esters oi hydroxy acids, o. 5.,

Esters iormed by substitution oi any of the "R" groups listed above (orone or more ol the acid hydrogen atoms of the following acids: 0 Lacticacid v Tartarlc acid Ricinoleic acid Hydroxy-stcaric acidHydrnxy-chlorstearic acid Cyclohcmnol carboxylic acids Hydroxybenwicacids Salicylic acid Hydroxy-phthaiic acids Hydroxy phcnyl-benzoic acidsNaphthol curboxylic acids 1 (2) Esters oi polyhydroxy alcohols andphenols in which at least one hydroxyl group remains unsubstituted, iorexan le, esters formed by esicriiying the (ol owing so that at least onehydroxyl group remains in the resulting ester:

Ethylene glycol Diethylene lyool Propylene g yools Butylenc glycolsPoly-hgdroxy benzenes Di droxy-benzenes esorcinol Catcchol HydroquinoneI Tri-hydroxyhcnzenes Pyroga 101 III. Sulphur-containing radicles, e.g.,

Any of the examples of oxy era-containing radicles in which at least oneoxygen atom as been replaced with sulphur. Specific examples orsulphur-containing radicles are: (A) 0! the thiocthyl typeThio-phenoxy-phenyl (CsHr-SC.H Thio-phenoxy-ethyl (CsHs-$-CrHr-)Thio-lauroxy-phenyl (CnHzs$C| 4) Thio-t-amyl-phenoxy-phcnyl (C H||-CH|S- CrHn CsHu Table II-Conttnued C 1H:- 8 C IHG'" '(B) 0!thelhio-ketone type Tho acetylhenyl. Th o-benzoy -pbenyl Th -o-stearol-phenyl T -o-napht enoyllion 1 Thio-stearoyl-cyclo exy (C) 01 thethio-cstcr type, c. g., derived from hydroxyesters of tbio-carboxylicacids. Examples oi such radicles are:

Where R is moth l, ethyl, butyl, amyl, lauryl,

stearoyl,napbt en 1, etc. (D) Radiclcs derived from ydroxy-organicpolysulphides by removal 0! the hydroxy group, a. g.,

l gig I i where R is hydrogen or an alkyl or cyclo-alkyl K P t lR-S.-R--

where R. is an alkyl or cyclo-alkyl group and R is an alkylene group.

where Y is a halogen, and A and .B' are either the same or differenthalogens, or the same or different radicles selected from the classconsisting of those having the formulas "XR and R where x is oxygen orsulphur and R is an organic radicle or hydrogen.

The reactant (b) will have the formula R'XH where R is an organicradicle and X is either oxygen or sulphur.

The pair of reactants (a) and (b) selected are such that at least one ofthem contains a. cycloaliphatic radicle; i. e., at least one of theradicles,

6 v R and R is a cycle-aliphatic radicle. Preferably the reactant (b) isone in which R is cycloaliphatic.

Examples of the reactant (a) are:

Phosphorus trichloride, PCla Phosphorus tribromide, PBra Compoundshaving the I formulas ROPQlz, (ROMPCI. RSPCh, (RShPCl, RPCiz and RaPClwhere R is an organic radicle selected from the list under Table II.

Specific examples of these compounds are those in which R is;

Phenyl Tolyl Xylyl Naphthyl Xenyl Ethyl phenyl Butyl phenyl Amyl phenylLauryl phenyl Cyclohexyl phenyl Naphthenyl phenyl Naphthenoyl phenylAmyl pctyl Lauryl Cyclohexyl Methyl cyclohexyl -Cyclohexyl-cyclohexylCertain compounds of the class having the formulas ROPCI: and (RO )2PC1may be prepared by adding an organic hydroxy compound slowly tophosphorous trlchloride in such proportions that the molecular ratio oforganic hydroxy compound to PC]: is two or less; Examples of such ireagents are those prepared by adding slowly to one mole of phosphorust-rlchloride one or two moles of a hydroxy-ester, such as, for example:

Trimethyl citrate Tributyl citrate Methyl lactate Ethyl lactate Butyllactate Lauryl lactate Cyclohexyl lactate Methyl salicylate La'urylsalicylate Cyclohexyl salicylate Examples of the reactant (b) are thosebetting the formula R'OH and R'SH, where R is any cyclo-aliphaticradicle selected from the list under Table II. Specific examples of suchcompounds are:

Cyclohexanol e Methyl cyclohexanols Dimethyl cyclohexanols Ethylcyclohexanols Propyl cyclohexanols Butyl cyclohexanols Amylcyclohexanols .Lauryl cyclohexanols Phenyl cyclohexanols Cyclohexylcyclohexanols Cyclohexyl carbinol Cyclopentanol Methyl-cyclopentanolCycloheptanol Decahydro-naphthols Tetrahydronaphthols Naphthenylalcohols those listed under Table II. Specific examples of reactant (b)to be used in this way are:

n-Octyl alcohol Capryl alcohol Lauryl alcohol Benzyl alcohol Phenolalcohol Cresols alcohol Amyl phenols Methyl lactate Methyl salicylateFrom the foregoing it will be observed that a very large number ofspecific addition agents are contemplated for use by this invention.This large number of specific materials may be conveniently divided intoa number of groups. The criteria which determine theallocation of aspecific material to a particular group may generally be considerationssuch as (a) the precise nature of the material, (b) the mode of itsmanufacture, and (c) its particular utility.

I shall therefore in the further identification of the numerous specificexamples contemplated for use refer to them by groups.

Group 1 The addition agents of this group may be subgenerically definedas the oil-soluble phosphorus bearing products resulting from thereaction of a trivalent phosphorus-and-halogen-containing compound witha material of the class consisting of cyclohexanol, homologs ofcyclohexanol, mixtures of cyclohexanol and its homologs, and mixtures ofhomologs of cyclohexanol.

Group 2 a The addition agents of this group may be subgenericallydefined as those which contain sulphur; for example the oil-solublephosphorusand-sulphur-containing products resulting from the reaction ofa trivalent phosphorus-andhalogen containing compound with a material ofthe class consisting of cyclohexanol, homologs of cyclohexanol, mixturesof cyclohexanol and its homologs, and mixtures of homologs ofcyclohexanol.

Group 3 The addition agents of this group may be subgenerically definedas those which contain a halogen; for example thephosphorus-and-chloripe-containing products resulting from the reactionof a trivalent phosphorus-and-halogen containing reagent withchlor-phenyl cyclohexanol.

Group 4 convenience in identification hereinafter referred to as P. C.Y. In the preparation of this material the commercial grade ofcyclohexanol may be employed since it contains in addition tocyclohexanol minor amounts of certain of the homologs such as methylcyclohexanol.

The relative proportions of this commercial grade of cyclohexanol andPC]; used in the preparation of P. C. Y. are given in the followingtable, as well as the properties of the end product:

cyclohexanol parts by weight 1215 PCh do.. 2655 Weight of product do2545 Weight of material removed by distillation -do 514 'Percent yieldbased on PCI; per cent 84 Percent yield based on CsHuOH do 88 Boilingpoint C 150-165 Melting point Liquid at room temperature Sp. gr. at 24 C1.06 Color Light yellow Phosphorus per cent-.. 11.6 Chlorine do 5.6 Acidnumber 166 Solubility:

H2O Insoluble Ethyl alcohol Completely miscible Mineral oil At least 5%The cyclohexanol is placed in a reaction vessel equipped with anagitator and reflux condenser. The vessel and agitator are preferably ofglass or enamel. The PC]: is added slowly and the temperature of thereactants maintained between 50 0. and 60 C. during the addition of thePC13. The mixture is stirred continuously during the addition of thePCla. The temperature of the reactants may be controlled by the rate ofthe addition of the PCla. After all of the PC]: has been added in themanner above described the reacting materials are heated in a water bathto 100 C. and then by use of such water'bath maintained at a temperatureof 100 C. for three hours. The reactants are mechanically agitatedthroughout the periods of addition of PCla; elevation to 100 C.; and thethree hour period while maintained at 100 C.

After being maintained at 100 C. for three hours the reaction materialis distilled at an absolute pressure of eight inches of mercury and allmaterials. boiling below 70 C. are discarded. A sharp break in the vaportemperature will be noted indicating completion of the distillation ofthe low boiling fraction and the fact that the residue is the endproduct suitable for use. The material which is distilled over isprobably largely minor amounts of unreacted PC13 and cyclohexanol. Ifdesired the end product may be water washed since such water washingstep will be found to remove a certain amount of chlorine which wouldotherwise remain. The properties of the composition given in theforegoing table are those for material which has been water washed.

We believe that the principal products of the reaction of PCla. with acompound of the class consisting of cyclohexanol and homologs ofcyclohexanol are esters of phosphorous acid (such as (ROMP, (ROMPOH andROP(OH) 2, where R is the cyclohexyl radicle or a homolog of it), andthat halogen-bearing derivatives of such esters may also be formed, aswell as other halogenbearing derivatives of ROH, for example RC1. Itappears that the phosphorus-bearing constitucuts of the reaction productare responsible for the stabilizing efiect when the product is used inaccordance with our invention. However, for most purposes, theotherconstituents are not deleterious, and for some purposes may even beadvantageously included, The phosphorus-bearing constituents are ingeneral much less volatile than the other constituents; the latter mayadjusted to maintain a value of 12.7 to 1'.

In the first test, a S. A. E. 20 motor oil having a viscosity index ofabout 105 was employed as the lubricant and in a second test, the sameoil to which .03% of P. C. Y. was added was employed as a lubricant. Theengine was fitted with new pistons and rings before the start of eachtest' and after completion of the first test, the engine therefore beeasily removed, if desired, by diswas taken down, thoroughly cleaned andfitted tillation at atmospheric or sub-atmospheric pres- 10 with a newpiston and rings. sure. At the conclusion of the first test, nearly theThe following table gives the results obtained entire skirt of thepiston was very black, while at by the addition of minor amounts of P.C. Y. prethe end of the second test only 60% of the skirt pared as aboveindicated to several different repshowed only very light deposits oflight brown resentative commercial oils and oils treated with material.The inside of the piston skirt at the other addition agents. end of thefirst test showed a light shellac-like Composition Oxidation testsConradson Q I Corro- Vis. in SUB at 210 F. Naphtha Insolubles E I NCarbon sion test, Hexachlor Ortho Math 1 Butyi Per 1 Lead- DiphenyiDir-blot swam? Stearent Bronze Oxide Benzene rate PCY o i Fm 1 O 1 At 48Pelr 'tcent H": for for weight r g. a r g. e.

r Hours Increase mg. 100 mg. 48 hrs.

MID-CONTINENT SAE 30 MOTOR 01L 1 (untreated) .32 1. e1 63. 1 74. 4 17. a1s. 5 44 121 1s 2 37 1.16 62. 9 68. 8 9. 4 2 5 2b) 41 16 27 1.30 63.567.9 6.9 24.0 b) 94 1. 82 63. 6 73. 1 16.0 17 46 111 51 45 1. 27 62. l67. 9 8. 3 22 (b) 79 22 41 2. 05 61. 6 72. 2 17. 2 13 118 02 40 1. 3062. l 69. 0 11. 1 28. 5 (b) 76 23 PENNSYLVANIA SAE 40 MOTOR 01L 1. 25 3.52 82. 7 104. 0 26. 3 (a (b; 5 08 1.26 2. 84. 3 95. 3 13. l (a b 3 31 1.46 2. 31 81. 8 95. 1 16. 3 ti) b 2 1. 67 3. 54 82. 3 104. 0 26. 5 a) 338 30 1.66 2. 61 82.1 95. 2 16. 0 a) (b 4 16 50 1. 19 2. 80 79. 6 98. 924. 2 Eli). (0g 6 1. 53 2. 41 81. 7 93. 6 g 14 6 a) (b 2 18'PENNSYLVANIA SAE 10 MOTOR OIL I I J.

.23 94 4a. 3 4o. 0 1. 0 0 b 54 .75 16 52 46. 1 47. 7 3. 5 43 b 12 15 .17.43 46.2 48.3 4.6 39 b N v .151' 15 1. 40 46,3 50. 6 9. 3 22 b 65 1. 40.22 .58 46.1 47.5 3.0 34.5 b 12 --.22 .21 1.19 46.5 50. 0 7. 5 23.0 (b85 40 18 55 46. 1 47. 5 3. 0 41. 0 (b 14 23 z,

I (0) did not produce 10 mg. inngliours. (b) did not produce 100 mg. in48 hrs.

The determinations which appear in the foredeposit with a dark browndeposit on the vertical. going table such as, for example, Conradsonribs while the inside of the pisto skirt at the end carbon, viscositydeterminations, and naphtha) oi the second test showed no di coloration.insoluble, were determined on samples prepared -7 In general,thematerials I thisdnvention will by an oxidation test procedure which isin every not be found incompatible ith common y emrespect similar tothat prescribed by the Standployed anti-oxidants such as are used ingasolines ard of Indiana oxidation test, excepting that a and the like.piece of iron wire is submerged in the oil during In general, we havefound that the materials the test. The data given in the column headedof the present invention do not detrimentally aicorrosion" has beendetermined in accordance fect the extreme pressure characteristics of awith'the standard Shell corrosion test using lead mineral lubricatingoil, for example, which char-1,, bronze as the metal. acteristics arethe result of the presence therein The effectivenessof P. C. Y. inimproving the o! the extreme pressure addition a'gents abovepropertiesof a lubricating composition for use in 6 named. Moreover, where th ematerials of the internal combustion engines with particularrepresent'invention have been tested in lubricating gard to thestability of the lubricant during use compositions which alsocontainmertain other adhas been demonstrated by tests conducted on adition agents, the extreme. pressure characterliquid-ceoled singlecylinder 4-cycle gasoline enistics of the resultant composition" hasbeen somegine rated at 2 /2 H. P. at 1800 R. P. M. This what improvedandsuch improvement has been engine was run at 1600 R. P. M. under a loadof traceable to the presence therein ot the com- 2 H. P. for a period of100 hours for each test. pounds ofthe present invention.

The coolingfiuid temperature was maintained at Throughout the foregoingspecification and in 250 F. and-the 'temperatureof-the lubricant in theappended claims, reference is made to "oilthe crankcase "at, 225v Theair-fuel ratio was 591 11216 and by such term, as used herein, it is 11intended to indicate the ability of the thus defined material to formnot only true solutions with the oil to which the same are added, butalso the ability to form therewith any form of substantially permanentlyhomogeneous composition.

As indicated above, my invention also contemplates the production anduse of oil-soluble derivatives of the compounds above specificallyidentified. Such derivatives include the oil-soluble salts andester-salts which may be produced by substituting a metal or basicradicle for one or more of the alcohol derived radicles of the immediatereaction product'of P013 and the alcohol. This is convenientlyaccomplished by partly or completely saponifying such reaction product Iwith an alkali (e. g., sodium potassium, ammonium or substitutedammonium hydroxide) in aqueous solution. Similar salts and ester-saltsof metals other than the alkyl metals may be formed directly by reactingsaid immediate reaction product with the metallic base, or more readilyby double decomposition of the alkyl salt (or ester-salt) with a salt ofthe other metal.

The reaction product of P013 prepared in the manner above described isfor certain uses preferable over pure tricycloh'exyl phosphite.

It will be found that the products resulting from the reaction of P013with homologs of cyclohexanol and particularly mixtures of such homologsand mixtures of such homologs with cyclohexanol will produce materialswhich are quite preferable over the remaining compounds of the classpreviously identified. The halogen-containing reaction products, whethersuch halogen is present as a result of the P013 reaction or introducedby direct halogenation, will be found to give decidedly improvedresults. In view of the character of the reaction products of PC]; withthe homologs of cyclohexanol as well as the halogen-bearing derivativesabove referred to, they may be employed in concentrations considerablygreater than those previously specified for the entire class ofcompounds wh ch may be employed as addition agents to lubricatingcompositions.

Throughout the foregoing description where halogens have been referredto, it is to be understood that the chlorinated species are very muchpreferred although the brominated and fluorinated species will also befound to have utility for particular uses.

The materials to which this invention relates have been found to beparticularly effective in preventing corrosion when added to lubricantsand fuels employed in internal combustion engines. They have been foundto be particularly effective as corrosion inhibitors when added toengine fuels such as gasoline which normally tend to show corrosiveeffects in which the fuel is burned.

Attention is directed to the fact that I am filing even date herewith anapplication Serial No. 424.824, which relates to these same materialsand it is intended that this application include all of the disclosureof such other application filed even date herewith insofar as thepresent case does not include the disclosures of such other case. Thisapplication is a continuation-in-part of my co-pending applicationSerial No. 265.051, filed March 30. 1939, now Patent No. 2290,8'72.

Other modes of ap lying the principle of my invention may be employedinstead of the one explained, change being made as regards thecomposition and method herein disclosed, provided 12 the ingredients orsteps stated by any of the following claims or the equivalent of suchstated ingredients or steps be employed.

I therefore particularly point out and distinctly claim as my invention:

1. A lubricating composition comprising principally a liquid hydrocarbonof the character which is normally subject to deterioration especiallyat high temperatures and when in contact with metals, and which has beenstabilized against such deterioration by the inclusion therein of aminor amount, sufficient to effect such stabilization, of a mixturephosphorus-containing compounds, which mixture consists of at least apart of the reaction product of (a) a trivalentphosphorus-and-halogen-containing reagent containing an organic radicleselected from the class consisting of aromatic and aliphatic radicleswith (b) a cycloaliphatic compound containing the XH group where X is anelement selected from the class consisting of oxygen and sulphur, saidreaction product prepared by mixing the reactants and exposing themixture to reaction conditions which produce the primaryreaction productwithout any substantial decomposition of such primary reaction product.

2. A lubricating composition comprising principally a liquid hydrocarbonof the character which is normally subject to deterioration especiallyat high temperatures and when in contact with metals, and which has beenstabilized against such deterioration by the inclusion therein of a 1minor amount, sufficient to effect such stabilization, of an organiccompound having the follow-,

ing structure:

wherein X is an element of the class consisting .organic radicleselected from the class consisting of aromatic and aliphatic radiclesand X is selected from the class consisting of oxygen and sulphur.

5. A lubricating composition in accordance with claim 1 in which (b) isa cycloaliphatic alcohol.

6. A lubricating composition in accordance with claim 1 in which (1)) isan alcohol containing the cyclohexyl nucleus.

7. A lubricating composition in accordance with claim 1 in which (b) isa substituted cyclohexyl alcohol.

8. A lubricating composition in accordance with claim 1 in which (b) isa cycloaliphatic ester.

9. 'A lubricating composition in accordance with claim 1 in which (b) isa cycloaliphatic mercaptan.

10. A lubricating composition in accordance with claim 1 in which (b) isa mercaptan containing a cyclohexyl nucleus.

11. A lubricating composition in accordance with claim 1 in which (a) isthe reaction product 13 of trimethyl citrate with phosphorus trichlorideand (b) is cyclohexanol.

12. A lubricating composition in accordance with claim 1 in which (a) isthe reaction product of methyl lactate with phosphorus trlchloride and(b) is cyclohexanol.

13. A lubricating composition comprising principally a liquidhydrocarbon of the character which is normally subject to deteriorationespecially at high temperatures and when in contact with metals, andwhich has been stabilized against such deterioration by the inclusiontherein of a minor amount, sufllcient to effect such stabilization, of amaterial 01' the class consisting of (1) a mixture ofphosphorus-containing compounds, which mixture consists of at least apart of the reaction product of (a) a trivalentphosphorusand-halogen-containing reagent containing an organic radicleselected from the class consisting of aromatic and aliphatic radicleswith (b) a compound of the class consisting of cycloallphatic hydroxyand cycloaliphatic mercapto compounds said reaction product prepared bymixing the reactants and exposing the mixture to reaction 14 conditionswhich produce the primary reaction product without any substantialdecomposition of suclrprimary reaction product, (2) salts derived irom(1), and (3), halogen-bearing derivatives of (1) and (2).

DELTON R. FREY.

REFERENCES CITED The following references are of recordin the file ofthis patent:

UNITED STATES PATENTS Schreiber Nov. 5, 1940

